This application is a 371 of PCT/EP98/00201, filed on Jan. 29, 1998.
The present invention relates to solid mixtures based on sulfonylureas and adjuvants.
Sulfonylureas (hereinafter referred to as xe2x80x9cSUsxe2x80x9d) are a group of highly active herbicides which are used widely in crop protection.
Since SUs are taken up through the leaves, SU activity can be improved by adding surfactants such as wetting agents to the spray liquor (cf. Green et al., ANPP, Seizixc3xa8me confxc3xa9rence du columaxe2x80x94Journees internationales sur la lutte contre les mauvaises herbes 1995, p. 469-474; xe2x80x9cDPX-KG 691xe2x80x94A new surfactant for sulfonyl urea herbicidesxe2x80x9d).
Particularly suitable wetting agents described in the literature are, inter alia, oil adjuvants (Nalejewa et al., Weed Technol. 9 (1995), p. 689-695) or alcohol ethoxylates (see above and Dunne et al., Weed Science 42 (1994), p. 82-85; Green, Weed Technol. 7 (1993), P. 633-640). In agricultural practice, these substances are added by the farmer as tank mix additives to the spray liquor. The mixture of SU herbicide and surfactant is prepared in the spray tank just prior to use.
For example, a double pack is commercially available under the trade name CATO(copyright) (Du Pont de Nemours), comprising 25% strength water-dispersible granules of the active compound rimsulfuron (component A) and a wetting agent (component B) which is separately packed and comprises a mixture of 2-butoxyethanol, polyethoxylated tallowamine and nonylphenyl polyethylene glycol ether. For use, the two components are mixed in the spray tank as described above.
In practice, it would be desirable to be able to use ready-to-use formulations already comprising an activity-increasing wetting agent to avoid the problematic mixing immediately prior to use. In this way, it would be possible to avoid logistical problems and mixing mistakes when preparing the spray liquor. Furthermore, solid formulations are generally advantageous from a technical point of view when designing and disposing of the packaging. It is further known from the literature that SU formulations are problematic with respect to the stability of the active ingredients since, under unfavorable conditions, they may decompose over time with loss of the desired herbicidal activity. The tendency to decompose also causes problems with respect to the registration requirements, since the stability of active crop protection compounds in formulations has to meet certain minimum requirements for registration.
JP-A 62/084004 describes the use of calcium carbonate and sodium tripolyphosphate for stabilizing SU formulations.
JP-A 63/023806 claims to solve the problem by using specific carriers and vegetable oils for preparing solid SU formulations. JP-A 08/104603 describes similar effects when epoxydated natural oils are used. A common feature of these two applications is the incorporation of vegetable oils into the solid formulation to make use of the activity-enhancing properties of these adjuvants, in addition to achieving an improved stability.
Vegetable oils are incorporated into liquid formulations (generally suspension concentrates) to utilize similar effects (cf. EP-A 313317 and EP-A 554015).
It is also known from the prior art to use alkylpolyglucosides as wetting agents/adjuvants.
WO 95/2841 provides solid mixtures of an active compound and an alkylpolyglucoside adsorbed on a carrier.
EP-A 498 154 describes solid formulations of alkylpolyglycosides with the active compound N-phosphonomethylglycine.
It is an object of the present invention to provide SU solid formulations which include the adjuvant from the start and which are superior to the solid formulations of the prior art.
We have found that this object is achieved by solid mixtures comprising
a) a sulfonylurea and
b) an adjuvant from the group of the alkylpolyglycosides.
Surprisingly, it was found that the use of alkylpolyglycosides as wetting agents in SU solid formulations results in a pronounced stabilization of the active ingredient in comparison to other wetting agents (for example ethoxylated fatty amines or alcohol ethoxylates). This effect can be observed especially when water-soluble inorganic salts, such as ammonium sulfate, are present in addition to herbicidally active compounds. The stabilization is especially pronounced when the wetting agent is employed at the concentration required for biological activity.
Storage-stable ready-to-use formulations having good biological activity are obtainable by mixing the SU with other active compounds, alkylpolyglycosides and ammonium sulfate.
The invention further provides processes for preparing the solid mixtures according to the invention and their use as crop protection agents for controlling undesirable harmful plants.
Suitable sulfonylureas a) are generally compounds having the structural unit 
Preference is given to SUs of the following structure I: 
where J is: 
xe2x80x83where the substituents R to R18 are:
R: H or CH3;
R1: F, Cl, Br, NO2, C1-C4-alkyl, C1-C4-haloalkyl, C3-C4-cycloalkyl, C2-C4-haloalkenyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C2-C4-alkoxyalkoxy, CO2R12, C(O)NR13R14, SO2NR15R16, S(O)nR17, C(O)R18, CH2CN or L;
R2: H, F, Cl, Br, CN, CH3, OCH3, SCH3, CF3 or OCF2H;
R3: Cl, NO2, CO2CH3, CO2CH2CH3, SO2N(CH3)2, SO2CH3, SO2CH2CH3, OCH3, or OCH2CH3;
R4: C1-C3-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C2-C4-haloalkenyl, F, Cl, Br, NO2, CO2R12, C(O)NR13R14, SO2NR15R16, S(O)nR17, C(O)R18 or L;
R5: H, F, Cl, Br or CH3;
R6: C1-C4-alkyl, C1-C4-alkoxy, C2-C4-haloalkenyl, F, Cl, Br, CO2R12, C(O)NR13R14, SO2NR15R16, S(O)nR17, C(O)R18 or L;
R7: H, F, Cl, CH3 or CF3;
R8: H, C1-C4-alkyl or pyridyl;
R9: C1-C4-alkyl, C1-C4-alkoxy, F, Cl, Br, NO2, CO2R12, SO2NR15R16, S(O)nR17, OCF2H, C(O)R18, C2-C4-haloalkenyl or L;
R10: H, Cl, F, Br, C1-C4-alkyl or C1-C4-alkoxy;
R11: H, C1-C4-alkyl, C1-C4-alkoxy, C2-C4-alkoxy; haloalkenyl [sic], F, Cl, Br, CO2R12, C(O)NR13R14, SO2NR15R16, S(O)nR17, C(O)R18 or L;
R12: C1-C4-alkyl, with or without substitution by halogen, C1-C4-alkoxy or CN, allyl or propargyl;
R13: H, C1-C4-alkyl or C1-C4-alkoxy;
R14: C1-C4-alkyl;
R15: H, C1-C4-alkyl, C1-C4-alkoxy, allyl or cyclopropyl;
R16: H or C1-C4-alkyl;
R17: C1-C4-alkyl, C1-C4-haloalkyl, allyl or propargyl;
R18: C1-C4-alkyl, C1-C4-haloalkyl or C3-C5-cycloalkyl, with or without substitution by halogen;
n is 0, 1 or 2;
L has the structure II 
xe2x80x83where
Rj: H or C1-C3-alkyl;
W: O or S;
X: H, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-haloalkyl, C1-C4-haloalkylthio, C1-C4-alkylthio, halogen, C2-C5-alkoxyalkyl, C2-C5-alkoxyalkoxy, amino, C1-C3-alkylamino or di(C1-C3-alkyl)amino;
Y: H, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, C2-C5-alkoxyalkyl, C2-C5-alkoxyalkoxy, amino, C1-C3-alkylamino, di(C1-C3-alkyl)amino, C3-C4-alkenyloxy, C3-C4-alkanyloxy [sic], C2-C5-alkylthioalkyl, C2-C5-alkylsulfinylalkyl, C2-C5-alkylsulfonylalkyl, C1-C4-haloalkyl, C2-C4-alkenyl, C3-C5-cycloalkyl, azido, fluorine or cyano;
Z: CH or N;
and agriculturally useful salts thereof.
Below, some suitable SUs are listed by their INN (International Nonproprietary Name) according to the Pesticide Manual:
ACC 322140;
Amidosulfuron;
Azimsulfuron (N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-1-methyl-4-(2-methyl-2H-tetrazol-5-yl)-1H-pyrazole-5-sulfonamide);
Bensulfuron-methyl (methyl 2-[[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]methyl]benzoate);
Ethyl 2-[[[[(4-chloro-6-methoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]benzoate (chlorimuron ethyl);
2-Chloro-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]benzenesulfonamide (chlorsulfuron);
Chlorsulfoxim;
Cinosulfuron;
Cyclosulfamuron;
Ethametsulfuron-methyl (methyl 2-[[[[[4-ethoxy-6-(methylamino)-1,3,5-triazin-2-yl]amino]carbonyl]amino]sulfonyl]benzoate);
Ethoxysulfuron;
Flazasulfuron;
Flupyrsulfuron (methyl 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-6-(trifluoromethyl)-3-pyridinecarboxylate);
Halosulfuron-methyl;
Imazosulfuron;
Methyl 2-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]benzoate (metsulfuron methyl);
nicosulfuron (2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-N,N-dimethyl-3-pyridinecarboxamide);
Oxasulfuron;
Primisulfuron (methyl 2-[[[[[4,6-bis(difluoromethoxy)-2-pyrimidinyl]amino]carbonyl]amino]sulfonyl]benzoate);
Prosulfuron;
Pyrazosulfuron-ethyl (ethyl 5-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-1-methyl-1H-pyrazole-4-carboxylate);
Rimsulfuron (N-[[(4,6-dimethoxy-2-pyrimidinylamino]carbonyl]-3-(ethylsulfonyl)-2-pyridinesulfonamide);
Sulfosulfuron;
Sulfometuron-methyl (methyl 2-[[[[(4,6-dimethyl-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]benzoate);
Thifensulfuron-methyl (methyl-3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]-2-thiophenecarboxylate);
2-(2-Chloroethoxy)-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]benzenelsulfonamide (triasulfuron);
Tribenuron-methyl (methyl 2-[[[[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N-methylamino]carbonyl]amino]sulfonyl]benzoate); and
Triflusulfuron-methyl (methyl 2-[[[[[4-(dimethylamino)-6-(2,2,2-trifluoroethoxy)-1,3,5-triazin-2-yl]amino]-carbonyl]-amino]sulfonyl]-3-methylbenzoate).
Particular preference is given to sulfonylureas of the formula III (equivalent to the formula I where J=J1) as known, for example, from EP-A 388 873, EP-A 559 814, EP-A 291 851 and EP-A 446 743: 
where:
R1 is C1-C4-alkyl, which may carry from one to five of the following groups: methoxy, ethoxy, SO2CH3, cyano, chlorine, fluorine, SCH3, S(O)CH3;
halogen;
a group ER19, in which E is O, S or NR20;
COOR12;
NO2;
S(O)nR17, SO2NR15R16, CONR13R14;
R2 is hydrogen, methyl, halogen, methoxy, nitro, cyano, trifluoromethyl, trifluoromethoxy, difluoromethoxy or methylthio,
Y is F, CF3, CF2Cl, CF2H, OCF3, OCF2Cl, C1-C4-alkyl or C1-C4-alkoxy;
X is C1-C2-alkoxy, C1-C2-alkyl, C1-C2-alkylthio, C1-C2-alkylamino, di-C1-C2-alkylamino, halogen, C1-C2-haloalkyl, C1-C2-haloalkoxy,
R is hydrogen or methyl;
R19 is C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl or C3-C6-cycloalkyl, each of which may carry from 1 to 5 halogen atoms. Furthermore, in the case that E is O or NR20, R19 is also methylsulfonyl, ethylsulfonyl, trifluoromethylsulfonyl, allylsulfonyl, propargylsulfonyl or dimethylsulfamoyl;
R20 is hydrogen, methyl or ethyl;
R12 is a C1-C4-alkyl group which may carry up to three of the following radicals: halogen, C1-C4-alkoxy, allyl or propargyl;
R17 is a C1-C4-alkyl group which may carry from one to three of the following radicals: halogen, C1-C4-alkoxy, allyl or propargyl;
R15 is hydrogen, a C1-C2-alkoxy group or a C1-C4-alkyl group;
R16 is hydrogen or a C1-C4-alkyl group,
R13 is H, C1-C4-alkyl or C1-C4-alkoxy,
R14 is C1-C4-alkyl,
n is 1 or 2,
Z is N, CH.
Particularly preferred sulfonylureas of the formula III are those of the general formula I where J is J1 and the remaining substituents have the following meanings:
R1is CO2CH3,CO2C2H5, CO2iC3H7, CF3, CF2H; OSO2CH3, OSO2N(CH3)2, Cl, NO2, SO2N(CH3)2, SO2CH3 and N(CH3)SO2CH3,
R2 is hydrogen, Cl, F or C1-C2-alkyl,
Y is CF2H, OCF3, OCF2Cl, CF2Cl, CF3 or F,
X is OCH3, OC2H5, OCF3, OCF2Cl; CF3, Cl, F, NH(CH3), N(CH3)2 or C1-C2-alkyl,
R5 is hydrogen, and
Z is N or CH.
particular preference is given to those compounds of the formula (IV) which are listed in the table below.
Table
Of course, component a) may also be a mixture of more than one sulfonylureas.
Component b) of the solid formulations according to the invention comprises one or more alkylpolyglycosides (referred to as APG below). Depending on the chemical structure and on the way the synthesis is carried out, the substance class of the APGs is referred to in the literature as alkylglucosides, alkylglycosides, alkylpolyglucosides or alkylpolyglycosides. Herewithin below, only the term APG will be used in lieu of all the other names, always referring to the entire group of the abovementioned compounds.
Especially preferred components b) are APGs having a mean degree of polymerization in the range from 1.0 to 6.0. They can be characterized by the formula II
R21O(Z)a
where R21 is an alkyl radical having from 4 to 30, preferably from 8 to 18, carbon atoms and Z is a glycoside radical having from 5 to 6 carbon atoms and a is a value in the range from 1 to 6, preferably from 1.0 to 1.7. Corresponding products are commercially available, inter alia under the names Agrimul(copyright) PG, APG(copyright), Plantaren(copyright) or Glucopon(copyright) (all by Henkel), Lutensol(copyright) (BASF), Atplus(copyright) (ICI Surfactants) or Triton(copyright) (Union Carbide).
Specific examples are:
Agrimul(copyright) PG 2067: an APG having a C8-C10-alkyl group and an average degree of polymerization of 1.7;
APG(copyright) 425: an APG having a C8-C16-alkyl group and an average degree of polymerization of 1.6;
APG(copyright) 625: an APG having a C12-C16-alkyl group and an average degree of polymerization of 1.6;
APG(copyright) 300: an APG having a C8-C16-alkyl group and an average degree of polymerization of 1.4;
AG 6202: an APG having a 2-ethylhexyl chain (Akzo Nobel) and an average degree of polymerization of 1.6;
Lutensol(copyright)GD 70: an APG having a C10-C12-alkyl group (BASF AG) and an average degree of polymerization of 1.3;
Agrimul(copyright) PG 2069: an APG having a C9-C11-alkyl group and an average degree of polymerization of 1.6;
Glucopon(copyright) 600: an APG having a C12-C16-alkyl group and an average degree of polymerization of 1.4;
Plantaren(copyright) 1300: an APG having a C12-C16-alkyl group and an average degree of polymerization of 1.6.
Other preferred APGs are Atplus(copyright) 258, Atplus(copyright) 264, Atplus(copyright) 430, Atplus(copyright) 460, Atplus(copyright) 469 and Atplus(copyright) 450 (alkyl polysaccharide/adjuvant blends, ICI Surfactants) and to Agrimul(copyright) PG 215, Agrimul(copyright) PG 600, Triton(copyright) BG-10 and Triton(copyright) CG-110.
Rather than unbranched alkyl radicals, particular preference may be given to branched alkyl radicals.
The percentage of the component a) in the solid mixtures according to the invention is generally in the range from 0.5 to 75% by weight, preferably from 1 to 25% by weight, based on the total weight of the formulation.
The percentage of the APGs (component b)) is generally in the range from 1 to 75, in particular from 1 to 50, especially from 5 to 25, % by weight, based on the total weight of the formulation.
In addition to the components a) and b), the solid mixtures according to the invention may comprise further active compounds which are miscible with sulfonylureas and/or produce synergistic effects. The corresponding products are known to the person skilled in the art and are described in the literature. The following groups of other active compounds are listed as examples under their INNs:
cl: 1,3,4-thiadiazoles:
buthidazole, cyprazole;
c2: amides:
allidochlor (CDAA), benzoylprop-ethyl, bromobutide, chlorthiamid, dimepiperate, dimethenamid, diphenamid, etobenzanid (benzchlomet), flamprop-methyl, fosamin, isoxaben, monalide, naptalame, pronamid (propyzamid), propanil;
c3: aminophosphoric acids:
bilanafos (bialaphos), buminafos, glufosinate-ammonium, glyphosate, sulfosate;
c4: aminotriazoles:
amitrol;
c5: anilides:
anilofos, mefenacet, thiafluamide;
c6: aryloxyalkanoic acids
2,4-D, 2,4-DB, clomeprop, dichlorprop, dichlorprop-P, (2,4-DP-P), fenoprop (2,4,5-TP), fluoroxypyr, MCPA, MCPB, mecoprop, mecoprop-P, napropamide, napropanilide, triclopyr;
c7: benzoic acids:
chloramben, dicamba;
c8: benziothiadiazinones [sic]:
Bentazon;
c9: bleachers:
clomazone (dimethazone), diflufenican, fluorochloridone, flupoxam, fluridone, pyrazolate, sulcotrione (chlor-mesulone) isoxaflutol, 2-(2xe2x80x2-chloro-3xe2x80x2-ethoxy-4xe2x80x2-ethylsulfonyl-benzoyl)-4-methyl-cyclohexane-1,3-dione;
c10: carbamates:
asulam, barban, butylate, carbetamide, chlorbufam, chlorpropham, cycloate, desmedipham, diallate, EPTC, esprocarb, molinate, orbencarb, pebulate, phenisopham, phenmedipham, propham, prosulfocarb, pyributicarb, sulfallate (CDEC), terbucarb, thiobencarb (benthiocarb), tiocarbazil, triallate, vernolate;
c11: quinolinic acids:
quinclorac, quinmerac;
c12: chloroacetanilides:
acetochlor, alachlor, butachlor, butenachlor, diethatyl ethyl, dimethachlor, dimethenamide (cf. also under category c2), metazachlor, metolachlor, pretilachlor, propachlor, prynachlor, terbuchlor, thenylchlor, xylachlor;
c13: cyclohexenones:
alloxydim, caloxydim, clethodim, cloproxydim, cycloxydim, sethoxydim, tralkoxydim, 2-{1-[2-(4-chloro-phenoxy) propyloxyimino] butyl}-3-hydroxy-5-(2H-tetrahydrothiopyran-3-yl)-2-cyclohexen-1-one;
c14: dichloropropionic acids:
dalapon;
c15: dihydrobenzofuranes:
ethofumesate;
c16: dihydrofuran-1-ones:
flurtamone;
c17: dinitroanilines:
benefin, butralin, dinitramin, ethalfluralin, fluchloralin, isopropalin, nitralin, oryzalin, pendimethalin, prodiamine, profluralin, trifluralin;
c18: dinitrophenoles:
bromofenoxim, dinoseb, dinoseb-acetat, dinoterb, DNOC;
c19: diphenyl ethers:
acifluorfen-sodium, aclonifen, bifenox, chlornitrofen (CNP), difenoxuron, ethoxyfen, fluorodifen, fluoroglycofen-ethyl, fomesafen, furyloxyfen, lactofen, nitrofen, nitrofluorfen, oxyfluorfen;
c20: bipyridyliums:
cyperquat, difenzoquat-methylsulfat, diquat, paraquat-dichlorid;
c21: ureas:
benzthiazuron, buturon, chlorbromuron, chloroxuron, chlortoluron, cumyluron, dibenzyluron, cycluron, dimefuron, diuron, dymron, ethidimuron, fenuron, fluormeturon, isoproturon, isouron, karbutilat, linuron, methabenzthiazuron, metobenzuron, metoxuron, monolinuron, monuron, neburon, siduron, tebuthiuron, trimeturon;
c22: imidazoles:
iscarbamide;
c23: imidazolinones:
imazamethapyr, imazapyr, imazaquin, imazethabenz-methyl (imazame),imazethapyr, imazamox;
c24: oxadiazoles:
methazole, oxadiargyl, oxadiazone;
c25: oxiranes:
tridiphane
c26: phenols:
bromoxynil, ioxynil;
c27: phenoxypropionic esters
clodinafop, cyhalofop-butyl, diclofop-methyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, fenthiapropethyl, fluazifop-butyl, fluazifop-p-butyl, haloxyfop-ethoxyethyl, haloxyfop-methyl, haloxyfop-p-methyl, isoxapyrifop, propaquizafop, quizalofop-ethyl, quizalofop-p-ethyl, quizalofoptefuryl;
c28: phenylacetic acids:
chlorfenac (fenac);
c29: phenylpropionic acids:
chlorophenprop-methyl;
c30: protoporphyrinogene IX oxydase inhibitors:
benzofenap, cinidon-ethyl, flumiclorac-pentyl, flumioxazin, flumipropyn, flupropacil, fluthiacet-methyl, pyrazoxyfen, sulfentrazone, thidiazimine, carfentrazone, azafenidin;
c31: pyrazoles:
nipyraclofen;
c32: pyridazines:
chloridazon, maleic hydrazide, norflurazon, pyridate;
c33: pyridinecarboxylic acids:
clopyralid, dithippyr, picloram, thaizopyr;
c34: pyrimidyl ethers:
pyrithiobac-acid, pyrithiobac-sodium, pyriminobac-methyl, bispyribenzoxim, bispyribac-sodium;
c35: sulfonamides:
flumetsulam, metosulam, cloransulam-methyl, diclosulam;
c36: triazines:
ametryn, atrazin, aziprotryn, cyanazine, cyprazine, desmetryn, dimethamethryn, dipropetryn, eglinazin-ethyl, hexazinon, procyazine, prometon, prometryn, propazin, secbumeton, simazin, simetryn, terbumeton, terbutryn, terbutylazin, trietazin, dimesyflam;
c37: triazinones:
ethiozin, metamitron, metribuzin;
c38: triazolecarboxamides:
triazofenamid;
c39: uracils:
bromacil, lenacil, terbacil;
c40: various:
benazolin, benfuresate, bensulide, benzofluor, butamifos, cafenstrole, chlorthal-dimethyl (DCPA), cinmethylin, dichlobenil, endothall, fluorbentranil, mefluidide, perf luidone, piperophos, diflufenzopyr, diflufenzopyr-sodium
or the environmentally compatible salts of the abovementioned groups of active compounds.
Other, preferred active compounds c) are, for example,
bromobutide, dimethenamide, isoxaben, propanil, glufosinate-ammonium, glyphosate, sulfosate, mefenacet, thiafluamide, 2,4-D, 2,4-DB, dichlorprop, dichlorprop-P, dichlorprop-P(2,4-DP-P), fluoroxopyr, MCPA, mecoprop, mecoprop-P, dicamba, bentazon, clomazone, diflufenican, sulcotrione, isoxaflutole, phenmedipham, thiobencarb, quinclorac, quinmerac, acetochlor, alachlor, butachlor, metazachlor, metolachlor, pretilachlor, butroxydim, caloxydim, clethodim, cycloxydim, sethoxydim, tralkoxydim, 2-{1-[2-(4-chlorophenoxy) propyloxyimino]butyl}-3-hydroxy-5-(2H-tetrahydrothiopyran-3-yl)-2-cyclohexen-1-one, pendimethalin, acifluorfen-sodium, bifenox, fluoroglycofen-ethyl, fomesafen, lactofen, chlortoluron, cycluron, dymron, isoproturon, metabenzthiazuron, imazaquin, imazamox, imazethabenz-methyl, imazethapyr, bromoxynil, ioxynil, clodinafop, cyhlaofop-butyl, fenoxyprop-ethyl, fenoxaprop-p-ethyl, haloxyfop-p-methyl, cinidon-ethyl, flumiclorac-pentyl, carfentrazone, flumipropyn, fluthiacet-methyl, pyridate, clopyralid, bispyribac-sodium, pyriminobac-methyl, flumetsulam, metosulam, atrazin, cyanazine, terbutylazine, benazolin, benfuresate, cafenstrole, cinemthylin, ammonium-bentazon, cloquintocet, diflufenzopyr, diflufenzopyr-sodium, pyraflufen-ethyl.
Particular preference is given to the following compounds c):
2,4-D, dichlorprop-P, MCPA, mecoprop-P, dicamba, bentazon, diflufenican, sulcotrione, quinclorac, caloxydim, cycloxydim, sethoxydim, 2-{1-[2-(-(4-chlorophenoxy)propyloxyimino]butyl}-3-hydroxy-5-(2H-tetrahydrothiopyran-3-yl)-2-cyclohexen-1-one [sic], acifluorfen-sodium, fluoroglycofen-ethyl, bromoxynil, fenoxyprop-ethyl, cinidon-ethyl, atrazin, terbutylazin, ammonium-bentazon, cloquintocet, thiafluamid, isoxaflutole, diflufenzopyr, diflufenzopyr-Na, carfentrazone, imazamox.
Very particular preference is given to the following compounds c):
2,4-D, dichlorprop-P, mecoprop-P, MCPA, ammonium-bentazon, bentazon, diflufenican, quinclorac, 2-{1-[2-(-(4-chlorophenoxy)propyloxyimino]butyl}-3-hydroxy-5-(2H-tetrahydrothiopyran-3-yl)-2-cyclohexen-1-one [sic], caloxydim, cycloxydim, sethoxydim, fluoroglycofen-ethyl, cinidon-ethyl, atrazin and terbutylazine, dicamba, diflufenzopyr, diflufenzopyr-Na.
The percentage of the other active compounds c), if present, is generally in the range from 0.5 to 75, preferably from 1 to 60, % by weight of the formulation.
In addition to the components a), b) and c) described above, the solid mixtures according to the invention may also contain customary formulation auxiliaries.
Suitable surfactants are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, for example ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids of arylsulfonates, of alkyl ethers, of lauryl ethers, of fatty alcohol sulfates and of fatty alcohol glycol ether sulfates, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, condensation products of phenol or of phenolsulfonic acid with formaldehyde, condensation products of phenol with formaldehyde and sodium sulfite, polyoxyethylene octylphenyl ethers, ethoxylated isooctyl-, octyl- or nonylphenol, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated triarylphenols, salts of phosphorylated triarylphenolethoxylates, polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin-sulfite liquors or methylcellulose or mixtures thereof.
The percentage of any surfactants used is generally in the range from 0.5 to 25% by weight, based on the total weight of the solid mixture.
The solid mixtures according to the invention may also be used together with carriers. Examples of carriers include: mineral earths such as silicas, silica gels, silicates, talc, kaolin, attaclay, limestone, chalk, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, thiourea and urea, products of vegetable origin such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders, attapulgites, montmorillonites, mica, vermiculites, synthetic silicas and synthetic calcium silicates or mixtures thereof.
Further additives which may be used in customary amounts are:
water-soluble compounds or salts, such as:
sodium sulfate, potassium sulfate, sodium chloride, potassium chloride, sodium acetate, ammonium hydrogen sulfate, ammonium chloride, ammonium acetate, ammonium formate, ammonium oxalate, ammonium carbonate, ammonium hydrogen carbonate, ammonium thiosulfate, ammonium hydrogen diphosphate, ammonium dihydrogen monophosphate, ammonium sodium hydrogen phosphate, ammonium thiocyanate, ammonium sulfamate or ammonium carbamate;
binders, such as:
polyvinylpyrrolidone, polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, carboxymethylcellulose, starch, vinylpyrolidone/vinyl acetate copolymers and polyvinyl acetate or mixtures thereof;
lubricants, such as:
Mg stearate, Na stearate, talc or polyethylene glycol or mixtures thereof;
defoamers, such as:
silicone emulsions, long-chain alcohols, phosphoric esters, acetylene diols, fatty acids or organofluorine compounds, and
complex formers, such as:
salts of ethylenediaminetetraacetic acid (EDTA), salts of trinitrilotriacetic acids or salts of polyphosphoric acids or mixtures thereof.
The solid mixtures according to the invention can be prepared in the form of powders, granules, briquettes, tablets and similar formulation variants. In addition to powders, particular preference is given to granules. The powders can be water-soluble or water-dispersible powders. The granules can be water-soluble or water-dispersible granules for use in spray application or granules for spreading for direct application. The mean particle size of the granules is generally between 200 xcexcm and 2 mm.
The resulting granule formulations are dust-free, free flowing, non-caking products which dissolve or disperse readily in cold water.
Owing to their properties, the products can easily be packaged in relatively large amounts. In addition to packages such as sacks or bags made of plastic, paper or laminated material, they can be handled in cardboard boxes or other bulk containers. To further reduce the exposure of the user, it is possible to package the products in water-soluble film-bags, such as, for example,polyvinyl alcohol film-bags, which can be placed directly into the spray tank, where they dissolve. Suitable water-soluble films are, inter alia, polyvinyl alcohol or cellulose derivatives, such as methylcellulose, methylhydroxypropylcellulose or carboxymethylcellulose. By portioning the product into quantities suitable for use, the user no longer comes into contact with the product. The water-soluble bags are preferably packaged in a water-vapor-impermeable outer wrapper, such as polyethylene film, polyethylene-laminated paper or aluminum foil.
The solid formulations according to the invention can be prepared by various processes known to the person skilled in the art.
Preferred preparation processes for the mentioned formulations are extruder granulation, spray drying, fluidized-bed agglomeration, mixer granulation and disk granulation.
Fluidized-bed granulation is particularly suitable. Depending on the desired composition of the formulation, an aqueous solution, emulsion or suspension containing all the ingredients of the recipe is sprayed into a fluidized-bed granulator and agglomerated.
If desired, it is also possible to initially introduce active compound salts and/or inorganic ammonium salts into the granulator and to spray them with a solution or emulsion/suspension of the remaining ingredients of the recipe to agglomerate them. Furthermore, it is possible to apply aqueous solutions, emulsions or suspensions containing specific ingredients of the recipe in succession to granules of the active compound, to an active compound salt and/or to an inorganic ammonium salt to obtain different coating layers.
In general, the granules are dried sufficiently during the fluidized-bed granulation. However, it may be advantageous to carry out a separate drying step in the same or in a separate drier after the granulation. Following the granulation/drying, the product is cooled and sieved.
A further particularly suitable process is extruder granulation. Extruder granulation is preferably carried out using a cage extruder, radial extruder or dome extruder with minimum compaction of the granulated pellets.
For granulation, a mixture of solids is premixed in a suitable mixer with a granulation liquid until an extrudable material is obtained. This is then extruded in one of the above-mentioned extruders. For extrusion, hole sizes from 0.3 to 3 mm are used (preferably 0.5-1.5 mm). Suitable mixtures of solids are mixtures of active compounds, formulation auxiliaries and, if appropriate, water-soluble salts. In general, these are preground. Sometimes it is sufficient to pregrind only the water-insoluble substances in suitable mills.
Suitable granulation liquids are water, the APGs according to the invention or aqueous solutions thereof. Aqueous solutions of inorganic salts, nonionic surfactants, anionic surfactants, solutions of binders such as polyvinylpyrrolidone, polyvinyl alcohol, carboxymethylcellulose, starch, vinylpyrrolidine/vinylacetate copolymers, sugars, dextrin or polyethylene glycol. After extruder granulation, the resulting granules are dried and, if required, sieved to remove particles which are too coarse or too fine.